An improved thermal decomposition method is used to prepare modified titanium base anode. Some researches have been carried out to learn about the oxygen evolution properties of RuMn, RuCo, RuCe and RuEu etc. in H2SO4 solution and their effect on the electrooxidation of methanol if added into the catalytic layers of Pt/Ti electrodes. The result indicates that the Pt/Ti electrodes containing RuMn, RuCo and RuEu etc. metal oxide catalysts with the powerful evolution property exhibit a higher electro-catalytic activity towards methanol electrooxidation than Pt/Ti electrodes without composite metal oxide catalysts.